Production of halogenated hydrocarbons



" sulfuric acid catalyst.

A still further object of this invention is the production of ahaloalkylcycloallcane by condensation of an alkyl halide and acyclo-olefin in Patented Apr. 3% W46 o-FFlCE' arcane PRODUCTION OFGENATED HYDRGCARBONS Louis Schmerling, Riverside, lit, assignor toUniversal Oil Products Company, Chicago, 111, a

corporation of Delaware No Drawing. Application July 29, 1943,

1 Serial No. 49%563 4 Claims. Cl. 260-658) This invention relates to thecondensation of a saturated halide and an oiefln or halo-olefin toproduce a higher boiling saturated halide or halogenated saturatedhydrocarbon. More speciflcally the process is concerned with thecondensation 01 a haloalkane or halocycloalkane and an olefinichydrocarbon or halo-Olefin in the presence of a sulfuric acid catalyst.

By the term condensation used in thisspeciflcat-ion and in the claims, Imean the chemical combination or a saturated halide (comprisinghaloalkanes and halocycloalkanes) and an olefin or halo-oleiln toproduce a higher boiling halogen-containing compound with a molecularweight equal to the sum of the molecular weights or said saturatedhalide and olefin or of said seturated halide and halo-olefin An objectof this invention is the condensation in the presence of a sulfuric acidcatalyst of a saturated organic halide and a member selected from thegroup consisting of oleilns and halo-olefins.

Another object or this invention is the condensation in the presence ofa sulfuric acid catalyst of a haloallrane or halocycloalkane and amember selected from the group consisting of olefins and halo-olefins toproduce higher boiling halogenated hydrocarbons.

A further object of this invention is the production of a higher boilingmonohaloalkane .by the condensation of a lower boiling alkyl halide andan oleflnic hydrocarbon in the presence of a the presence of a sulfuricacid catalyst.

' In one specific embodiment the present invention comprises a processfor condensing alkyl I halides with olefinic hydrocarbons orhalo-olefins in the presence'oi' a sulfuric acid catalyst toproducehisher boiling: allsyl halides or dihaloalkanes.

In a further embodiment the present invention comprises a process forcondensing a halocycloparaiiln and an olefin or halo-olefin in thepresence of a sulfuric acid catalyst to produce a higher cloparaiiin.

Saturated organic mouohalide's which'may be reacted with oleiins orhaio-oleilns according to the process of'this invention include alkylhalides ferred for use in condensation reactions with oleof varioushigher molecular weight halogen-containing compounds. Examples ofchlorides which are especially useful in the process 01 thi inventionare tertiary butyl chloride, tertiary amyl boilinghalcallcylcycloparafiin or dihalo-allcylcyand halocycioparafiins whichmay also be referred to as monohaloalkanes and monohalocycloailranes.respectively. In general, tertiary halides V I are preferred :to primaryand secondary halides.

fihlorides and bromides are-also generally preride, etc.

" gaseous olefinic hydrocarbons.

chloride, 1 chloro l methylcyclopentane, 1- chloro-l-methylcyclohexane,and 9-ch10rodecahydronaphthalene.

Some alkyl halides and cycloalkylhalides are produced by addition of ahydrogen halide such as hydrogen chloride or bromide to a mono-oleflnichydrocarbon or cyclo-oleflnic hydrocarbon. said addition reaction beingeifected generally in the presence of a catalyst such as aFriedel-Crafts type metal halide, an acid such as sulfuric acid.phosphoric acid, etc. Such an addition of a hydrogen halide to an olefinresults in the production of secondary alkyl halides from nontertiaryoleflns containing three or more carbon atoms per molecule and in theformation aftertiary alkyl halides from tertiary oleilns such asisobutylene, trimethyl ethylene, etc. Primary alkyl halides also utillzable in the present process tor producing higher boiling alkyl halidesare obtainable by other means such .as the addition of a hydrogen halideto ethylene, the treatment of a primary alcohol with hydrogen halide inthe presence of a suitable catalyst such as zinc chlo- Primary alkylbromides may be obtained from a l-alkene oralpha-olefin by additionjofhydrogen bromide in the presence of peroxides or sunlight.

Olefinic hydrocarbons utilizable in the present process include olefinsand cyclo-olefins. The

.olefins may be either normally gaseous or normally liquid and compriseethylene, propylene. butylenes, and higher normally liquid oleiins, thelatter including various polymers of normally These aliphatic olefinichydrocarbons which are utilizable in the present process, although notat exactly the sam conditions of operation, may be obtained from anysource and particularly from the products of catalytic and thermalcracking of oils, by de' hydrogenation of paraidnic hydrocarbons, or bydehydratine alcohols.

Cyclo-olefinic hydrocarbons utilizable in the present process comprisecyclic hydrocarbons of the general formula CnHQm-B in which n'representsan integer which is at least 3 and preferably 5 or 6. Cyclopentene,alkylcyclopentene, cyclohexene, and alkylcyclohexenes are thecycleoleiins which I prefer to react with alkyl halides to producealkyl-cyclopentyl and alkyicyciohexylhalides including monoalkyl andpolyalkylcycloalkyl halides. Thus, a cycle-olefin and an alkyl halidecondense to form an alkylcycloalkyl halide while a monoalkylcyclo-oleilnand an alkyl halide react to form a dialkylcycloalkyi halide.Cyclopropene, cyclobutene, and alkylcyclobutenes are generally moredimcult to obtain than the cyclo-- Vinyl chloride, allyl chloride, allylbromide,

propenyl chloride, and isopropenyi chloride are representative ofsuitable halo-oleflns containing 1 halogen atom and 1 double bond permolecule and utilizable in the present process. The term "halo-oleflns"is used herein in reference to the above-mentioned unsaturated halogencompounds as well as to other unsaturated compounds such ashalocyclo-olefins containing one halogen atom and one double bond permolecule. Compounds containing one double bond and more than one halogenatom per molecule, and other compounds containing more than one doublebond and one or more chlorine or bromine atoms per molecule, may also beused in the process of the present invention, although not necessarilyunder the same conditions of operation.

Halo-oleflns may be formed in any suitable manner such as by the actionof a halogen upon an olefin at a temperature at which substitutionOccurs and at a temperature substantially in excess of that at which theprincipal reaction is addition of a halogen to the oleilnic doublebond.' They may also be prepared by the addition of a halogen toanoieflnic double bond to form a dihaloalkane from which one molecule ofhydrogen halide may be removed by any of several well known methods toproduce a haloolefin. Furthermore halo-oleflns may be pre-- pared byaddition of hydrogen halide to acetylenic hydrocarbons.

The concentration of the sulfuric acid which is used as catalyst willdepend in general on the particular saturated halide and oleflnichydrocarbon or halo-olefin charged to the condensation reaction. Ingeneral, the sulfuric acid concentration will be from about 85% to about100% H2804, but I prefer to employ sulfuric acid of about 96% H2804concentration particularly when charging oleilnic hydrocarbonscontaining at least four carbon atoms per molecule. How.- ever, whenpropylene or a halo-olefin containin I 3 carbon atoms per molecule isused as a reactant, it is generally preferable to use as catalyst asulfuric acid solution containing from about- 96 to about 100% H2804.

The process for condensing saturated halides with oleflns orcyclo-oleflns is apparently somewhat analogous to the, addition of ahydrogen halide to either of these unsaturated hydrocarbons. t is. thealkyl halide apparently adds to the double bond of the unsaturatedhydrocarbon producing another alkyl halide of higher molecular weight.For example, the condensationof tertiary butyl chloride with ethyleneproduces 4-chloro-2.2-dimethylbutane, which is a chloroneohexane, asillustrated by the following equation:

, CH: CH: Dark-4'11 HsC=CHa CHr-%CHr-CH CI CH: CHI

Tertiary butyl chloride undergoes similar condensations with propyleneand with n-butylene producing chloroheptane and chloro-octane. re.-spectively. Similarly bromoheptane may be obtained by the reaction oftertiary butyl bromide with propylene. Under some conditions thecombination of an alkyl halide with an olefin may be so controlled as togive other higher boiling alkyl halides containing all of the componentsof both the original olefin and lower boiling alkyl halide charged tothe process. y

In reactions between saturated halides and halo-oleilns it appears thata saturatedhalide adds to the double bond of a halo-olefin to produce adihaloalkane with a molecular weight equal to the sum of the molecularweights of the two reactants. For example, the-condensation of tertiarybutyl chloride with vinyl chloride produces1.1-dichloro-3,3-dimethylbutane, which is a dichloroneohexane. Thisreaction is illustrated by the following equation:

(CH3) sCCl+H2C=CHC1 (CHa aCCHrCI-ICI:

The dichlorohexaneindic'ated in thepreceding equation may be convertedinto 'neohexane.

tertiary butyl acetaldehyde, chlorohexen'e, or

other desirable compounds. The process of this invention thus teaches asimple method, for preparing compounds containing a quaternary carbonatom as well as of homologs of vinyl chloride.

The condensation of a saturated halide land a member selected from thegroup consisting of olefins and halo-oleilns is carried out bycontacting the reactants in the presence of sulfuric acid at atemperature of from about 40P.to about C. but preferably at atemperature of from about -l0 to about50 C. generally while maintaininga pressure sui'licient to keep in liquid statea substantial proportionof the reactants.

The reactions of different saturated halides with different oleilnic andhalo-oleflnic hydrocarbons are not necessarily carried out with equalease or at the same conditions of operation. Sometimes when theoperating temperature is higher than the preferred temperature,secondary reactions such as dehydrohalogenation and polymerizationbecome substantial.- Tertiary halides are more reactive with oieilns andhalo-oletins than are secondary halides. and in turn the secondaryhalides are more reactive than primary halides.

Accordingly, primary, secondary, and tertiary alkyl halides anddifferent halocycloalkanes are generally not utilizable under the sameconditions of operation.

-The reaction of a saturated halide with an olefin or halo-olefin may becarried out in the presence of sulfuric acid used in either batch orcontinuous types of operation. In batch type operation, desiredproportions of saturated halide (such as alkyl halide orhalocycloalkane) and an olefin or halo-olefin are introduced to asuitable reactor together with a sulfuric acid catalyst, and

' at a reaction temperature until a substantial proportion 01 thereactants are converted into the desired higher molecular weighthalogenated hydrocarbon. The reaction mixture after separation from thecatalyst is fractionated to separate the unconverted saturated halideand olefin or halo-olefin from the higher boiling halogenatedhydrocarbon, and the recovered reactants and catalyst may then be usedin another run to produce an additional quantity of the desiredhalogenated hydrocarbon.

Continuous operations may be carried out by conducting a mixture of asaturatedhalide and an olefin or halo-olefin through a reactor oisuitable design in the presence of sulfuric acid. In this type oftreatment, the operating conditions may be adjusted suitably, and maydifler somewhat from those employed in batch type operat on.

Insome cases it may be advisable to commingle thecharged alkyl halide orhalocycloalkane and olefin or halo-olefin with a substantially inertsolvent such as a parafiinic hydrocarbon, for example, normal pentane,andthen to effect condensation in the presence of this added solvent andof the sulfuric acid catalyst. Obviously the solvent chosen should beone which does not undergo undesirable reactions with the othercomponents of the reaction mixture under the operof 2 molecularproportions of tertiary butyl chlobons produced by the present processmay be used for various purposes. Some or them may be converted intohydrocarbons of high antiknock value, others may be used as solvents oremployed as I intermediate compounds in organic syntheses.

The following examples are given to illustrate the character of resultsobtained by the use of the present process, although the data presentedare not introduced with the intention of unduly trlestricting thegenerally broad scope of the inven- Example I as molecular proportionsof army-m1 chloride and 3.0 molecular proportions of propylene whenreacted at 10 C. for 2 hours in the presence of 1 molecular proportionof 100% sulfuric "acid gave 12% of the theoretical yield of achloroheptane boiling from 140 to 143 C., a 8% yield of chloroheptaneboiling at 1289-132 0., and in addltion a 20% yield of isopropylchloride formed ride and 1 molecular proportion of 96% sulfuric acid.From the resultant reaction product an 18% yield was obtained of achloro-octane boiling at 154-160 C. and a yield of secondary butylchloride. Thechloro-octane boiling at 154-160 C. was probably4-chloro-2,2,3-trimethylpentane.

The foregoing specification and examples illustrate the novelty andutility of the present invention, although neither section is introducedwith the intention of unduly limiting its generally broad scope.

' I claim as my invention:

l. A process for the production of monohaloalkanes which comprisesreacting a lower boiling tertiarymonohaloalkane with a mono-olefin inthe presence of a sulfuric acid catalyst at a temperature of from about10 C. to about 50 C. and a pressure sufiicient to maintain the reactantsin substantially liquid state and recovering from the resultant productsa higher boiling monohaloalkane having a molecular weight equal to thesum of the molecular weights of said lower boiling tertiarymon'ohaloalkane and said mono-olefin 2:. A process for the production ofmonochloroaikanes which comprises reacting tertiary butyl chloride witha mono-olefin in the presence of a sulfuric acid catalyst at atemperature of 10 C. and a pressure sufiicient to maintain'the reactantsin substantially liquid state and recovering from the resultant productsa higher boiling monoch1o-= roalkane having a molecular weight equal tothe sum of the molecular weights of said tertiary butyl chloride andsaid mono-olefin.

3. A process for the production of monochloroalkanes which comprisesreacting tertiary butyl chloride with propylene in the presence of asulfuric acid catalyst at a temperature of 10 C. and a pressuresufilcient to maintain the reactants in substantially liquid state andrecovering from the resultant products a higher boiling mono-- insubstantially liquid state and recovering from the resultant products ahigher boiling monochloroalkane having a molecular weight equal to thesum of the molecular weights of said tertiary butyl chloride and saidbutylene.

1 molecular proportion of butylene-2 was added at 10' C. during '3hours'to a well stirred mixture LOUIS SCHMERLING.

